Apparatus for continuous vacuum refining of sponge metallic titanium



March 17, 1959 HIROSHI ISHIZUKA V APPARATUS F0 Filed July 22, 1955 OFSPONGE METALLIC TITANIUM 2,878,008 R .commuous VACUUM REFINING '4Shee'ts-Sheet l IN V EN TOR.

H/ROJH/ I JH/ZUKA W F W A TTORNEYS.

March 17, 1959 APPARATUS F OF SPONGE METALLIC TITANIUM Filed July 22,195 5 4 Sheets-Sheet 2 F/LiE.

INVENTOR. H/ROSHI' lJH/Z UKA A TTORNEYS.

March 17, 1959 HIROSHI ISHIZUKA I 2,878,008 APPARATUS FOR commuousVACUUM REFINING OF SPONGE METALLIC TITANIUM Filed July 22, 1955 4Sheets-Sheet 3 I I Z? A is B 2 l j 21 Y A 7 8 B [5 1e 30 4; I INVENTOR.

H/ROJH/ IJH/ZU/FA BY y F A TTORNEYS.

March 17, 1959 HIROSHI ISHIZUKA 2,87

- APPARATUS FOR CONTINUOUS VACUUM REFININGY- Y 0F SPONGE METALLICTITANIUM Filed July 22, 1955 4 Sheets-Sheet 4 'F/EAZ,

INVEN TOR. H/ROJH/ lJl-l/Zl/KA BY we 5 ATTORNEYS.

United States APPARATUS FOR' CONTINUOUS VACUUM REFIN- ING F SPONGEMETALLIC TITANIUM Hiroshi Ishizuka, Ashiya-shi, Japan Application July22, 1955, Serial No. 523,859

2 Claims. (Cl. 266-16) i The present invention relates to an apparatusfor re- "fining spongeous titanium continuously under vacuum, moreparticularly to an apparatus for the continuous production of highpurity spongeous titanium by a process wherein titanium tetrachloride(TiCl is reacted with metallic magnesium (Mg) or sodium (Na) in areaction cylinder in accordance with the following equations:

I titanium'industrially is performed by reacting TiCl, with Mg or Na athigh temperatures in an inert gas atmosphere. In this process, the abovegiven reaction is carried out in a reaction cylinder, usually of iron,to collect therein spongeous titanium which adheres to the inner wall ofthe reaction cylinder. In the case in which Mg is used as the reducingagent in the above given reaction, an excess of Mg is used. As a result,the spongeous titanium obtained contains a small amount of unreactedmagnesium admixed therewith. The magnesium chloride (Mgcl obtained asby-product of the reaction cylinder is preferably removed from thebottom of the reaction, but there still remains a small amount of it inthe spongeous titanium. This magnesium chloride has to be removed.

The usual practice for this removal is the vacuum separation process.The present inventor also carries out this practice. That is, in theusual process the reaction cylinder in which TiCl, and Mg are reactedtogether consists of an innner cylinder and an outer cylinder. Spongeoustitanium precipitates and adheres to the inner wall of the innercylinder which is then cooled to a safe temperature. The cooled innercylinder is then inserted into the vacuum separation cylinder. Thevacuum separation cylinder is a top-sealed cylinder provided with acondensing portion underneath, i.e. an outer-separating cylinder. Thesaid inner cylinder containing therein spongeous titanium adherent tothe inner wall, is first placed into said outer separating cylinderwhich is then evacuated to high vacuum, e.g. 10- to mm. of Hg. Then, theouter-cylinder portion'corresponding to the in- -serted inner cylinderis heated exteriorly in a heating furnace at elevated temperatures, forexample, 900 to 1000 C. for more than twenty hours. The Mg and MgClcontained in the spongeous titanium are then volatilized and introducedinto the lower condensing portion wherein they are condensed andsolidified.

The resulting spongeous titanium then is of a high degree of purity.

After completionof the treatment, first the heating furnace is removedand cooled sufficiently. Thereafter,

atent thebute'r-separating cylinder is removed, and the inner cylindercontaining the adherent spongeous titanium' is shifted to peel off andcollect the spongeous titanium.

However, the spongeo'us titanium is apt to. come in contact with theambient air during the above given operation and the large surfaceareaof the'spongeous titanium is likely to be readily degraded by'reacting with oxygen, nitrogen, hydrogen, etc'. Thus, unless thespongeous titanium is rapidly cooled, it is likely to burn temperaturesbefore it is cooled to the temperature re quired by the prior artprocess. The said reaction receptacle is hung down Within a casing keptin vacuum or in inert gas atmosphere.

Or, the reaction inner receptacleencased in the'casing held at hightemperature and in vacuum or in inert gas,

e.g. argon atmosphere is lowered into the interior or the vacuumrefining apparatus according to this invention.

In the accompanying drawings given'as illustrationof the invention: 7

Fig. 1 is a sectional elevation of the apparatus illustrating the firstposition of said apparatus, where the upper portions of two outercasings have just been placed respectively on the corresponding. lowerportions of the casings after two pairs of lids have been closed;

Fig. 2 is a similar view of Fig. 1 illustrating the second position ofthe apparatus, where the two inner receptacles are descending to therespective bottoms of the vacuum distillation chamber and the condensingchamber, after the two pairs of lids have been removed laterally totheir casings; I

Fig. 3 is a view similar to Fig. 1 illustrating the third position ofthe apparatus, where the two innerreceptacles are set respectively intheir operative positions, the two hanging rods having been detachedfrom the respective top covers of the two inner receptacles and the twopairs of lids having been removed, ready for removing the two upperportions of the outer casings;

Fig. 4 is a view similar to Fig. 1 illustrating the fourth position(i.e. the working position), where the two upper portions'of the outercasings are removed and the distillation and the condensing apparatusesare in operation. (After completion, the above order is reversed.)

Referring to the drawings, for example, the inner receptacle casing 9holding the inner reaction receptacle at a high temperature in aninert-gas atmosphere, is placed on flange 24; the inner receptacle 2 islowered by actuating a lateral hanging metal 5 as well as a longitudinalhanging metal 6 and a hanging rod 10 and put into an outer separationreceptacle 4. The outer receptacle 4 is held in a heating furnace, andis adapted to be heated to the required temperature.

A bottom plate 3 for the inner receptacle is provided in the lowerportion of the inner receptacle 2. Spongeous titanium adheres to theinner wall of the inner receptacle above the bottom plate and forms inlump form. The inner receptacle 2 having been prepared for the vacuumdistillation treatment, that is, immediately after m e n of V the t qneact n... is. su p n ed. by means of hanging rod 10 (for innerreceptacle) in the I I tightened outer receptacle lid chamber 26,arrangedlaterally above outerreceptacle '4. The inner receptacle 2 1 iis then lowered as-lllustarted in the drawing by actuating "hanging rod10. and placed into outer receptacle 4. The; I

: outer receptacle lid '7 'is'then moved to makeasuificiently air-tightseal. Then the vacuum separation is carried out.

I I After the vacuum separation. treatment has been com- I pleted, theouter receptacle lid 7 'is opened and the inner I 1 receptacle isreaisedintothe inner:receptaclecasing; 9 I mounted above. The inner receptacleis sealed with the 'satio'n receptacle, lid is opened, the innercondensingre- I J Thus, the inner receptacle'zhavi ceptacle islowered'and lix'edand then the lid is shut and,

thecondensation isfurthercontinued, I 1

g spongeous titanium admixed with Mg a d MgCl is put into the outer re-,

1 ce'ptacle 4. When heating: is carried out at high tempera'tures, e. g.900. to 1000 (Lin high vacuum, for instance, of, 10- to mm. of Hg, Mgand MgC l 1 1 are volatilizedand enter into the inner condensationre'ceptacle 13- throughlsuction fine 11' and; are condensed f.

[and adhere in the inner condensation receptacle 13. I,

Heating elements 30 have beenadded in several loca I "tions in thedrawings for the sake of illustration. 1

1' transferred even while being kept at a: high temperature I I in an.inert gasatmosphere, directly to theapparatus for i I the vacuumrefining and-fixed. ;After highvacu'umand I I high temperature treatmenthas been completed and the bottom lid 8 for said casing and then itisseparated along I i line A-:,B and is shifted for the following step.

A suction gas line is provided on the side wall of outer I receptacle 4,whichleads to aninner condensing receptacle I 1,3 I tion-plate' 12 rsprovided so "that gases-I introduced by suction ,may be: setsufiicientlyin the condensing receptacle: 13 and condensed and that thecondensatemay be In said. inner condensing receptacle 13, a condensaprevented fromfalling in the suction flue .11.

' y In the gases separated by-suificient condensation in'thecondensinginner receptacle '13 in a condensation re t ceptacle,there is practically no solid substance, but in I some cases presumablythere maybe a small quantity of; solid materials. I In order to avoidthe above-said con- 'tamination, a lamellar preventing sheet'18 isprovided,

through which gases are passed and led to the vacuum pump.

When the sufficiently condensed and separated mixture of Mg and MgCl hasbeen sufficiently deposited in the condensation inner receptacle, theinner receptacle is required to be exchanged. For this purpose, acondensation inner receptacle casing 21 is provided, wherein thecondensation inner receptacle is suspended in airtightness. Thecondensation inner receptacle casing 21 is placed on the flange 25 online A'B. Then the condensation inner receptacle is suspended in saidcasing to be removed. A new inner receptacle is then suspended andinserted.

For example, in order to withdraw the inner receptacle 13 containing Mgand MgCl adherent therein, out of the condensation receptacle 14, thecondensation inner receptacle casing 21 is mounted along line A--B' anda vacuum is created in said casing. The lid 19 for condensing innerreceptacle casing 21 is shifted into the lid chamber 28 providedlaterally with a condensation inner receptacle lid which is arranged inair-tightness on the inner condensation receptacle and accommodated inthe position of inner condensation receptacle lid 19. The innercondensation cylinder 13 is attached after the hanging rod 22 isinserted and then is received by the inner condensation receptaclecasing. The lid is air-tightly sealed by shifting the casing bottom lid20 in the bottom lid chamber 29 for the inner condensing receptaclecasing, the casing whereupon is separated on the line A'-B' and isremoved.

Then, the inner condensing receptacle casing containing a new innercondensing receptacle is set on line A'-B' above the condensationreceptacle, the bottom lid for inner condensation receptacle is openedand the conden- 1 1 'Anoutlet 16 for suction gas is provided onthe'inner I receptacle .lid 151 for condensing on top of condensinginner receptacle'13, and the inner receptacle 13 is 'ap- I I propriatelysuspended by means ofhanging rod 22,-thus I being adapted to: be takenout of or inserted into the con- I 'densin'g receptacle 14; I I 1 1 1 II Thecondensing receptacle 14 can be cooledsufficiently by .acondensation cylinder 17." 1

According to this inventi0n,'as above-said; the reaction receptacle inwhichspongeous titanium adheres can be admixed MgQl has been 'gasifiedand separated, the

spongeous; titanium iswithdrawn andshifted adherent in, the reactionreceptacle at a high: temperature before it has'been cooled ton lowtemperature and the opera-I I I tionj can;thus' be carried; out:continuously. Moreover, the thus gasified Mg and Mg'Cl are condensed ina con I nected condensation receptacle and-are condensed and de I I 1posited intoa movable receptacle which is withdrawn and charged. Thevacuum separation is, thus, performed con tinuously. I

withdrawal of the inner receptacle for the vacuum sepaseparationreceptacle and'by performing the charging and "withdrawal of said. innerreceptacle under exclusion of I I contact'with atmospheric air; And astheinncr receptacle I is withdrawn and afresh receptacle is replaced,after the vacum treatment has been colmpl'etedflhe operation can be madecontinuously with out contact with the out;

side air.

Moreover, the condensation of vacuum separated Mg and MgCl is effectedin a connected condensation receptacle. The shifting of the receptacle,i. e., the condensation receptacle containing Mg and MgCl condensedtherein and adherent thereto, can be carried out continuously withoutallowing contact with the outside air as in the above mentioned caserelative to the inner receptacle.

The present invention relates to an apparatus wherein the usual batchprocedure is carried out continuously and rapidly while avoiding thedeterioration of the quality of the products. With this apparatus, ahigh grade product can be easily obtained industrially and economically.According to this apparatus, the absorption of O, N and H 0 does notoccur, the purity of product is high, the damage of pumps due to thepresence of HCl is low, economy in heat, labor and time can be achievedand the mass production of uniform products is assured at high yield.The apparatus according to this invention can be used for the vacuumseparation not only in connection with the reduction of TiCl, by Mg butalso with the reduction by means of Na.

The present invention which is applicable also to other similar metalsenables the continuous operation which has heretofore been consideredimpossible and aims particularly to provide continuous production oftitanium especially in. vacuum refining. Thus the great industrial valueof the present invention is readily ap parent.

What I claim:

1. Apparatus for continuous vacuum distillation which comprises, incombination, a distillation apparatus provided with an outer casing toaccommodate therein an According to the present invention, the chargingand' J ration can be carriedoutrapidly in vacuum or inertgas. atmosphereand can also be performed at elevated 'tem I per'atures by putting theinner 1 receptacle containing 'spongeous titanium therein adherent intothe vacuum inner receptacle in which the mixture to be subjected tovacuum distillation is contained therein adherent to the wall, a pair oflids provided above said inner receptacle when said inner receptacle isin its operational position within the distillation apparatus, said pairof lids being adapted to keep said outer casing air-tight, and aseparate condensation apparatus connected to said distillationapparatus, said condensation apparatus comprising an outer casing toaccommodate therein an inner receptacle, adapted to receive substanceswhich have been gasified by the vacuum distillation performed in saidvacuum distillation apparatus, a pair of lids provided above the lastmentioned inner receptacle when said last mentioned inner receptacle isin its operational position within the condensation apparatus, said lastmentioned pair of lids being adapted to keep the last mentioned outercasing air-tight, and there is provided a vacuum pump for evacuation,whereby said distillation apparatus and said condensation apparatus areconnected together, means adapted for mounting thereon an innerreceptacle encased in an inner receptacle casing and means forintroducing said inner receptacle into said distillation apparatus whilemaintaining exclusion of air from said distillation apparatus.

2. Apparatus for continuous vacuum distillation which comprises, incombination, a distillation apparatus provided with an outer casing toaccommodate therein as inner receptacle in which the mixture to besubjected to vacuum distillation is contained therein adherent to thewall, a pair of lids provided above said inner receptacle when saidinner receptacle is in its operational position within the distillationapparatus, said pair of lids being adapted to keep said outer casingair-tight, and a separate condensation apparatus connected to saiddistillation apparatus, said condensation apparatus comprising an outercasing to accommodate therein an inner receptacle, adapted to receivesubstances which have been gasified by the vacuum distillation performedin said vacuum distillation apparatus, a pair of lids provided above thelast mentioned inner receptacle when said last mentioned innerreceptacle is in its operational position within the condensationapparatus, said last mentioned pair of lids being adapted to keep thelast mentioned outer casing air-tight, and there is provided a vacuumpump for evacuation, whereby said distillation apparatus and saidcondensation apparatus are connected together, means for air-tightlyencasing an inner receptacle in a casing so as to permit the removal ofsaid inner receptacle encased in its casing from the distillationapparatus while maintaining exclusion of air from said distillationapparatus.

References Cited in the file of this patent UNITED STATES PATENTS

1. APPARATUS FOR CONTINUOUS VACUUM DISTILLATION WHICH COMPRISES, INCOMBINATION, A DISTILLATION APPARATUS PROVIDED WITH AN OUTER CASING TOACCOMODATE THEREIN AN INNER RECEPTACLE IN WHICH THE MIXTURE TO BESUBJECTED TO VACUUM DISTILLATION IS CONTAINED THEREIN ADHERENT TO THEWALL, A PAIR OF LIDS PROVIDED ABOVE SAID INNER RECEPTACLE WHEN SAIDINNER RECEPTACLE IS IN ITS OPERATIONAL POSITION WITHIN THE DISTILLATIONAPPARATUS, SAID PAIR OF LIDS BEING ADAPTED TO KEEP SAID OUTER CASINGAIR-TIGHT, AND A SEPARATE CONDENSATION APPARATUS CONNECTED TO SAIDDISTILLATION APPARATUS, SAID CONDENSATION APPARATUS COMPRISING AN OUTERCASING TO ACCOMDATE THEREIN AN INNER RECEPTACLE, ADAPTED TO RECEIVESUBSTANCES WHICH HAVE BEEN GASIFIED BY THE VACUUM DISTILLATION PERFORMEDIN SAID VACUUM DISTILLATION APPARATUS, A PAIR OF LIDS PROVIDED ABOVE THELAST MENTIONED INNER RECEPTACLE WHEN SAID LAST MENTIONED INNERRECEPTACLE IS IN ITS OPERATIONAL POSITION WITHIN THE CONDENSATIONAPPARATUS, SAID LAST MENTIONED OUTER CASING BEING ADAPTED TO KEEP THELAST MENTIONED PAIR OF LIDS AIR-TIGHT, AND THERE IS PROVIDED A VACUUMPUMP FOR EVACUATION, WHEREBY SAID DISTILLATION APPARATUS AND SAIDCONDENSATION APPARATUS ARE CONNECTED TOGETHER, MEANS ADAPTED FORMOUNTING THEREON AN INNER RECEPTACLE ENCASED IN AN INNER RECEPTACLECASING AND MEANS FOR INTRODUCING SAID INNER RECEPTACLE INTO SAIDDISTILLATION APPARATUS WHILE MAINTAINING EXCULSION OF AIR FROM SAIDDISTILLATION APPARATUS.